CN105859755A - 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and application - Google Patents

1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and application Download PDF

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CN105859755A
CN105859755A CN201610255184.5A CN201610255184A CN105859755A CN 105859755 A CN105859755 A CN 105859755A CN 201610255184 A CN201610255184 A CN 201610255184A CN 105859755 A CN105859755 A CN 105859755A
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dimethyl
ipa
triazole
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phthalic acid
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王中良
王英
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Tianjin University
Tianjin Normal University
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Abstract

The invention discloses a 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and a preparation method and application thereof. A structure is [Cd(L)(ipa)(H2O)] 1.5NMP 2.25H2O, wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; ipa=isophthalic acid; NMP=1-methyl-2-pyrrolidone. The invention also discloses the preparation method of the single crystal. The preparation method is a normal-temperature volatilizing method, comprising the following steps of stirring L, hipa and Cd(NO3)2 6H2O in a mixed solvent of water and NMP for 0.5h, filtering, and volatilizing a filtrate for two weeks at the normal temperature, so as to obtain the colorless blocky crystal which is suitable for X-ray single crystal diffraction, wherein the molar ratio of L:ipa:Cd(NO3)2 6H2O is 1:1:1. The invention further discloses the application of the 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal special for fluorophenylboronic acid to generate a 4,4'-difluorobiphenyl catalyst.

Description

The double triazole M-phthalic acid cadmium complex of 1,4-dimethyl-2,5-two-1H-1,2,4- Monocrystalline and application
The present invention obtains the subsidy of Tianjin innovation team of Education Commission (TD12-5037).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to Isosorbide-5-Nitrae-dimethyl-2,5-bis--1H-1,2,4-double three Azoles M-phthalic acid cadmium complex monocrystalline { [Cd (L) (ipa) (H2O)]·1.5NMP·2.25H2Preparation method and the conduct of O} are urged Application in terms of agent, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)-1H-1,2,4-tri- Azoles；Ipa=M-phthalic acid；NMP=1-Methyl-2-Pyrrolidone.
Background technology
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound the most.These parts can be former with the nitrogen on 1,2 Son forms N1, N2-bridging pattern with metallic ion coordination, can be by 2,4 for 4 unsubstituted 1,2,4-triazole derivatives On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension Metal complex has been the vital step of device.
The present invention is i.e. to use room temperature volatility process, i.e. L, ipa and Cd (NO3)2·6H2O is in the mixed solvent of water and NMP Stirring is filtered after half an hour, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction, structure after volatilizing two weeks For { [Cd (L) (ipa) (H2O)]·1.5NMP·2.25H2O}, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-tri- Azoles-1-base) phenyl)-1H-1,2,4-triazole；Ipa=M-phthalic acid；NMP=1-Methyl-2-Pyrrolidone.This coordination compound The catalyst being alternatively arranged as generating fluorobenzoic boric acid 4,4'-DfBP is applied.
Summary of the invention
Following technical scheme is current inventor provides for this:
A kind of Isosorbide-5-Nitrae-dimethyl-2,5-bis--1H-1, the monocrystalline of 2,4-double triazole M-phthalic acid cadmium complexes, it is characterised in that This mono-crystalline structures uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, λ=0.71073 For incident radiation, collect point diffraction with ω-2 θ scan mode, obtain cell parameter through least square refinement, from difference Fu Vertical leaf electron density map utilizes software to solve single crystal data:
Its structure is as follows:
{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Ipa=M-phthalic acid；
NMP=1-Methyl-2-Pyrrolidone.
The present invention further discloses the double triazole M-phthalic acid cadmium complex of 1,4-dimethyl-2,5-two-1H-1,2,4- The preparation method of monocrystalline, it is characterised in that it is to use room temperature volatility process, by L, ipa and Cd (NO3)2·6H2O is at water and NMP Filtering after stirring half an hour in mixed solvent, filtrate room temperature obtains being suitable for the colourless bulk of X-ray single crystal diffraction after volatilizing two weeks Crystal；Wherein L:ipa:Cd (NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole M-phthalic acid cadmium complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is { [Cd (L) (ipa)(H2O)]·1.5NMP·2.25H2O}；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) benzene Base)-1H-1,2,4-triazole；Ipa=M-phthalic acid；NMP=1-Methyl-2-Pyrrolidone；
L NMP。
The present invention further discloses the double triazole M-phthalic acid cadmium of 1,4-dimethyl-2,5-two-1H-1,2,4-and coordinates Thing monocrystalline specificity generates 4 to fluorobenzoic boric acid, and the catalyst of 4'-DfBP is applied, and experimental result shows:
(1) catalyst that the complex monocrystal specificity in embodiment 2 generates 4,4'-DfBP to fluorobenzoic boric acid has relatively Good catalytic effect, catalysis productivity reaches 96%；
(2) complex monocrystal is to 3-methoxyphenylboronic acid, 1-naphthalene phenylboric acid, 4-methylthio phenyl boric acid, 4-chlorophenylboronic acid, 4-pyrrole Pyridine phenylboric acid catalytic effect does not the most even react.
The double triazole M-phthalic acid cadmium complex list of a kind of 1,4-dimethyl-2,5-two-1H-1,2,4-disclosed by the invention Brilliant have the advantage that and feature are:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) the double triazole M-phthalic acid cadmium complex of the 1,4-dimethyl-2,5-two-1H-1,2,4-prepared by the present invention Monocrystalline, production cost is low, and method is easy, is suitable for large-scale production.In terms of catalysis generates 4,4'-DfBP to fluorobenzoic boric acid There is good catalytic effect.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The two-dimensional structure figure of Fig. 2: complex monocrystal；
Fig. 3: 4,4'-DfBP1H NMR schemes.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it Limit the scope of the present invention by any way.Raw materials used it is commercially available.All raw materials are all public from chemical reagent both domestic and external The raw materials such as department buys, such as Isosorbide-5-Nitrae-two bromo-2,5-dimethyl benzene, through continuation purification but directly do not use.
Embodiment 1
1,4-bis-bromo-2,5-dimethyl benzene: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1
Be separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer CuO (0.0398 mg, 0.5 mmol), potassium carbonate (2.0731 g, 15 mmol), 1H-1,2,4-triazoles (0.345 mg, 5 mmol), Isosorbide-5-Nitrae-two Bromo-2,5-dimethyl benzene (0.3360 g, 1 mmol), 20 mL NMP.Start stirring 100oC, reacts 24 hours.Reaction After end, reactant liquor being down to room temperature, filter, filtrate adds 100 mL water, separates out a large amount of precipitation, sucking filtration, collects filter cake, yield 60%.Elementary analysis (C12N6H12) theoretical value (%): C, 59.99；H, 5.03；N, 34.98.Measured value: C, 60.02；H, 5.05； N, 35.05；
1,4-bis-bromo-2,5-dimethyl benzene 1H-1,2,4-triazole.
The bromo-2,5-dimethyl benzene of the preferred 1,4-of the present invention bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1；Reaction temperature 80-200 DEG C, 12-120 hour response time.Use " one kettle way ", by bromo-for Isosorbide-5-Nitrae-two 2,5-bis- Methylbenzene and 1H-1,2,4-triazoles prepare this organic compound in a heated condition, 1-(2,5-dimethyl-4-(1H-1,2,4- Triazol-1-yl) phenyl)-1H-1,2,4-triazole (L).
Embodiment 2
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), Phthalic acid (ipa) (0.1 mmol) and Cd (NO3)2·6H2O (0.1 mmol) is at water (10 mL) and NMP (2 mL) Filtering after stirring half an hour in mixed solvent, filtrate room temperature obtains being suitable for the colourless bulk of X-ray single crystal diffraction after volatilizing two weeks Crystal.Productivity: 40%.Elementary analysis (C17H19N4O6Cd) theoretical value (%): C, 46.33；H, 4.35；N, 12.71.Measured value: C, 46.36；H, 4.25；N, 12.62.
Embodiment 3
Crystal structure determination uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ= 0.71073 is incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement, Software is utilized to solve crystal structure from difference Fourier electron density map, and through Lorentz lorentz and polarity effect correction.All of H is former Son is synthesized by difference Fourier and determines through preferable position calculation.Detailed axonometry data:
Embodiment 4
Specificity is as the concrete instance of catalyst
Method: fluorobenzoic boric acid (0.82 mmol) and cesium carbonate (0.01 g) are dissolved in 3 mL NMP by replacement, add 5 mg Catalyst, stirs 5 hours under room temperature, CH2Cl2Extraction, washing, it is dried, filters, precipitation, thick product is through petrol ether/ethyl acetate Mixed liquor (v:v=1:1) by silica gel chromatography post affords product.
Result: obtaining 4,4'-DfBP 0.0764 g, calculated catalysis productivity is 98%.
Embodiment 5
Conclusion:
(1) the double triazole M-phthalic acid cadmium complex of 1,4-dimethyl-2,5-two-1H-1,2,4-is for catalytic substrate 4-first sulfur Base phenylboric acid does not play any catalytic action.
(2) the double triazole M-phthalic acid cadmium complex of 1,4-dimethyl-2,5-two-1H-1,2,4-is for 3-methoxybenzene Boric acid, 1-naphthalene phenylboric acid, 4-chlorophenylboronic acid, 4-pyridine phenylboric acid catalytic effect general, catalysis productivity is between 2-11%.
(3) the double triazole M-phthalic acid cadmium complex of 1,4-dimethyl-2,5-two-1H-1,2,4-is for catalytic substrate 4- The catalytic effect of fluorobenzoic boric acid is best, and catalysis productivity is up to 98%.
After the preferred embodiment described in detail, it is familiar with this skilled worker and is clearly understood that, without departing from above-mentioned Can carry out various change and amendment under claim and spirit, all technical spirit according to the present invention are to above example institute Any simple modification, equivalent variations and the modification made, belongs to the scope of technical solution of the present invention.And the present invention is not illustrated The restriction of example embodiment in book.

Claims (3)

1. Isosorbide-5-Nitrae-dimethyl-2,5-bis--1H-1, the monocrystalline of 2,4-double triazole M-phthalic acid cadmium complexes, its feature exists Use APEX II CCD single crystal diffractometer in this mono-crystalline structures, use through graphite monochromatised Mok alpha ray, λ= 0.71073 is incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement, Software is utilized to solve single crystal data from difference Fourier electron density map:
Its structure is as follows:
{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Ipa=M-phthalic acid；
NMP=1-Methyl-2-Pyrrolidone.
2. 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 double triazole M-phthalic acid cadmium complex monocrystalline Preparation method, it is characterised in that it is to use room temperature volatility process, i.e. L, ipa and Cd (NO3)2·6H2O is molten in the mixing of water and NMP Filtering after stirring half an hour in agent, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks, Wherein L:ipa:Cd (NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole M-phthalic acid cadmium complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is { [Cd (L) (ipa)(H2O)]·1.5NMP·2.25H2O}；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) benzene Base)-1H-1,2,4-triazole；Ipa=M-phthalic acid；NMP=1-Methyl-2-Pyrrolidone；
L NMP。
3. the double triazole M-phthalic acid cadmium complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 is special Attribute generates the application in terms of the catalyst of 4,4'-DfBP to fluorobenzoic boric acid.
CN201610255184.5A 2016-04-25 2016-04-25 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and application Pending CN105859755A (en)

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CN110577474A (en) * 2018-06-11 2019-12-17 天津师范大学 Synthesis method and application of Cd (II) complex with three-dimensional porous structure

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CN104497018A (en) * 2014-12-15 2015-04-08 天津师范大学 Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex

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Publication number Priority date Publication date Assignee Title
CN110577474A (en) * 2018-06-11 2019-12-17 天津师范大学 Synthesis method and application of Cd (II) complex with three-dimensional porous structure
CN110577474B (en) * 2018-06-11 2022-05-31 天津师范大学 Synthesis method and application of Cd (II) complex with three-dimensional porous structure

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